Separation of phenols from thiophenols



June 15, 1954 v, HESS ETAL 2,681,369

SEPARATION OF' PHENOLS FROM THIOPHENOLS Filed' March 20, 1952 IN VEN TORS Ho WA @D Y Hess TTORNEY Patented June l5, 1954 SEPARATION F PHENOLS FROM THIOPHEN OLS Howard V. Hess, Glenham, and'EdWinUKnowles,"

Poughkeepsie, N. Y., assignors to The Texas 'f Company, Delaware New York, N. Y., .a corporation of Application March 20, 1952, Serial No. 277,644

14 Claims. l:

'Ihisinvention'relates tov a novel process for separatingphenolic compounds from` their sulfur analogs, namely, thiophenol and its homologs. Itiiis'particularly concerned with the separation of vlow molecular weight phenoliccompounds such as phenoL'cresols, ethylphenols and xylenols from tliiophenolic compounds with whichphenols are usually associated in'` natural sources such as coal tar; `shale oil., and :petroleum naphtha.

In.,copending'rapplications Serial No. 176,661,

SerialNc; 1316,6625xboth'ledronJuly29, 1950,l now U'. S.;Patents` 2,618,664and 2,618,665; respeetively, andfin SerialNo.` 226,644, led May 16, 1951, all or which'are filed in thenames of Howard V. Hess and George BfArnold; it isdisclosed that low molecular weight", phenolict compounds such as phenol;v cresols, ethylphenolsand xylenolsare separatecl:` from crude 'mixtures containing higher molecular Aweight phenolic compounds and nonphenolic'fcompcunds byl contact with'` hexazfnethn yleneftetramine rinithei presence'of an` antisolvent whereby` there is formed .a liquid complex phase which isinsolublefinlthe antisolvent solution of thephen'olic compound-containingmixture. The liquidacomplexiphase which comprises :complexes ofhexamethylene tetramine `with phenol, cresols, ethylphenols and,r xylenolsy separates from the antisolvent solution;l and is decomposedinto its components by contact `with an oxygenated. hy-

drocarbon solvent fsuch `asaether whichu Vextracts thephenolic'compoundsfrom the complex'phase. Aparainic hydrocarbon or amixture of' parainic and/ornaphthenic hydrocarbonsiis employed as `the f anti-solvent ywithl apentane fraction being a particularly preferred i antisolvent.

The vsubject` invention involves the surprising discovery that complexing;` action of hexarnethylene tetraminein the presence of an antisolvent is specific to low molecular weight phenolic compounds so that separation of low molecular weight phenols from-,thiophenolic compounds can be effected therewith.` Since thiophenolic compounds are more highly acidic the corre sponding phenolic compounds, it was particularly surprising to discover that a basic complexing agent suchas hexamethylene tetramine in the `presence of an anti-solvent was able todistinguish between phenol and itstmore acidicanalog, thiophenol. The discovery that a mixture of phenols and thiophennls is readily separated into:` phenolic and thiophenclic components by the use `ofCnexarnethylene tetraminein conjunction with anantisolvent is of substantial import, since sep- -arationzof Vphenols from thiophenols by `presently availableriprocedures is troublesome and Vconsumes substantial quantities .of chemicals.A

In accordance'with the process ofthis invention, low'molecularweight phenolic compounds suchas phenol, cresols; ethylphenols andfxylenols are separated `fronrthiophenol and its homologs bycontacting a mixture containingboth phenols and thiophenols with hexamethylene tetramine in the presence' lof an antisolventwhereby thereis formed aliquidr'complex'phase which is insoluble in the antisolvent solution and is readily separated therefrom; Afterseparation of the liquid complex phase,` which comprises complexes of hexainethyleney tetra-lnine'with phenol, cresolsv, ethylphenolsand xylenols, it is Vwashed"'with antisolvent and then decomposed into its components by extraction with an oxygenatedf hydrocarbon solvent whereby there is-` formed hexamethylene tetramine and an' extract phasecontaining low molecular weight phenols which are substantially free from thiophenoliccontaminants; Thethiophenolic componentsfof the voriginal mixture are recoveredA` from `the antisolventV solution of Mcrude mixture `and fromthe Wash solution obtained by washingV the `complex phaseprior to `its decomposition. A parainic-hydrocarbon, a naphthenic hydrocarbonor a mixtureof ysuch hydrocarbons is employed asi the antisolvent; apentane fraction is a particularly preferred antisolvent. Con'- tact of the fphenoland thiophenol-containing mixture with hexamethylenetetramine is normally eiiected Yin the presence of `an antisolvent, but it is possible to effect the` Contactin.l the absence of the antisolvent andl subsequently add antisolvent -W-ith the resulting separation of i the complexphasef Decomposition of the separated liquid complex phase is eilectedfbyextraction withfan oxygenated hydrocarbon solvent such as` ether and tetrahydrofurane.

Contact-oie the aromatic` mixture containing low molecular` weight phenols-andthiophenols with hexamethylene tetramine is ordinarily effected4 at atmosphericrtemperature, but theupper allowable temperature is .approximately F. Decomposition` of the Vseparated complex phase with an oxygenated hydrocarbon solvent for recovery of lowf molecular weight `phenols is also efiectedat temperatures below 180"\14".`

Solid anhydrous hexamethylenetetramine in powder form or aqueous hexamethylene tetramine in the form of a solution or slurrycan be employed: as theV complexing agent. When solidsanlhydrous hexamethylene tetramine is vern-- ployed as the-complexing agent, there is a solids handling problem'in that the -two-phase-mixture comprising liquidA complexphase and anti-solvent solutionV of f aromatic mixture mustl be separated byt'iiltration or fdecantation "from the excess solid tion is realized. The invention will be described hereafter with aqueous hexamethylene tetramine as the complexing agent.

Phenol, cresols and xylenols, which are important commercial chemicals because of their extensive use in the manufacture of resins, dyes,

pharmaceuticals and petroleum additives, are obtained mainly from natural sources such as coal tar, wherein they are associated with thiophenolic compounds. Because of the similar chemical nature of phenols and thiophenols, the former processes employed to isolate phenolic compounds from coal tar and other sources fail to differentiate between these compounds with the result that the recovered product is a mixture vof both phenolic and thiophenolic compounds. .These normal procedures employed for recovery of phenolic compounds involve extraction with solvents such as solutions of caustic soda, sodium carbonate and sodium sulfide, aqueous alcohol,

pyridine sulfate solution, rormic acid solution and solutions of sodium phenolate.

The resolution of the product obtained by these common solvent extraction processes into phenols and thiophenolic compounds has been troublesome. but necessary, since many of the contemplated uses of the low molecular weight phenols preclude the presence of thiophenols which are highly odoriferous compounds. Moreover, thiophenols are in demand as chemical intermediates in the preparation of lube oil additives. The process of this invention provides a simple means for resolving a mixture of phenolic and thiophenolic compounds into its components and is, consequently, a signicant contribution to the eld of aromatic chemistry.

The process of this invention is only applicable to the separation of low molecular weight phenolic compounds which term is specically used to describe phenol, itself, cresols ethylphenols and xylenols from thiophenolic compounds. is apparent that the primary usefulness of the process of the invention is separating these low molecular weight phenolic compounds from thiophenolic compounds of similar molecular weight and of corresponding similar boiling point; separation of low molecular weight phenols from high molecular weight thiophenolic compounds is lnormally effected on the basis of boiling point. The process of the invention may also be used to separate an individual phenolic compound from its thiophenolc analog, for example, to separate phenol from thiophenol or cresols from thiocresol.

The complexing agent employed in the process of this invention is hexamethylene tetramine, a well known and commercially available condensation product of formaldehyde and ammonia. Hexamethylene tetramine is employed medicinally under the name of Urotropin.

The antisolvent whose presence causes separation of a liquid complex phase from the crude aromatic mixture is a paraffinic hydrocarbon which is advantageously an aliphatic hydrocarbon containing 3 to l()` carbon atoms. When normally gaseous aliphatic hydrocarbons, such as propane and butane, are employed as antisolvents, it is necessary to employ a pressure system. Pentanes and hexanes are particularly preferred antisolvents, since they are easily recovered from the aromatic mixture. Naphthenes such as cyclohexane and cyclopentane are effective antisolvents. Mixtures of parainic hydrocarbons such as straight run naptha and petrol ether may also be employed as the antisolvent. Ordinarily, an equal volume of antisolvent is added to the phenoland thiophenol-containing mixture, but the volume ratio of antisolvent to crude aromatic mixture may vary between 0.5 and 5 with high volume ratios being used when the phenolic content of the acid oil is low' and low volume ratios when the phenolic content is high. s

Contact of the antisolvent solution of phenoland Vthiophenol-containing aromatic mixture with aqueous hexamethylene tetramine must be effected at a temperature below 180 F. in order to avoid resin formation. Usually contact of the aromatic mixture and hexamethylene tetramine is effected at temperatures between 50 and 120 F. Since formation of the complex phase and its separation from the aromatic mixture are apparently not effected by pressure, atmospheric pressure is normally used, although both subatmospheric and superatomspheric pressures may be employed. Superatmospheric pressures are prescribed when a normally gaseous hydrocarbon such as propane is employed as the antisolvent.

A number of diierent procedures may be employed to contact the antisolvent solution of aromatic oil and aqueous hexamethylene tetramine. A preferred procedure involves countercurrent contact or" antisolvent solution of aromatic oil and aqueous hexamethylene tetramine in a tower. This type system is equivalent to a countercurrent extraction system and results in excellent separation of low molecular weight phenols from thiophenols in a single pass. Batch-wise operation in mixing vesselsequipped with agitators may also be employed, but it does not possess the eiiiciency of countercurrent tower contacting. A contact time adequate to assure substantially complete complex formation is desired; 10 to 20 minutes of contact time has been found adequate for complex formation and separation of complex from the antisolvent solution containing thiophenols and aromatic oil.

It is necessary to wash separated complex phase with antisolvent in order to remove dissolved aromatic mixture therefrom. In a countercurrent system this washing is simply effected by introduction of the antisolvent into the contacting tower at a point below where the aromatic oil is introduced so that complexing and washing are effected in a unitary operation.

Ordinarily, decomposition of the complex phase is eected in the presence of the aqueous phase which is either a solution or slurry of complexing agent. When the combined complex and aqueous phases are subjected to contact with ether, the complex is decomposed with a liberation of low molecular weight phenols which dissolve in the ether and with the liberation of hexamcthylene tetramine which is taken up in the aqueous phase. Decomposition of the complex is advantageously effected by a countercurrent exfferred solvents furane.

*tractionoperation wherein the :combined complex 'and aqueous phases are contacted countercurrently with ether with the resultingdecomposition of the complex `and extraction of liberated llowmolecular weight phenols in the Vether extract phase. When the complexes are decomposed in the presence of the aqueous phase, there is no -oi the liquid complex phase with ether. The

vac'ivantages `of eiiecting decomposition in the presence of an aqueous phase are apparent, since *such treatment eliminates handling of solid hex- `amethylene tetramine.

Decomposition of the complex `phase may be effected with oxygenated compounds, such as aliphatic ethers and cyclioethers, and, in general,

with those oxygenated solvents which have a high solvent power for phenols and a low solvent power for hexamethylene tetramine and for water. In addition, water is a suitable solvent for decomposition of the complex if the phenols `involved in the complex are substantially insoliible in water. Since water decomposes the complex by dissolving the hexamethylene tetramine `portion thereof, it is apparent that it may only be employed where the complex phase comprises Vsubstantially water-insoluble phenols, such as xylenols and ethylphenols. Particularly preare diethyl ether and tetrahydro- Decomposition of the complex by contact with ether or water is eected at Itemperatures below 180 F. in order to avoid resin formation. The

usual temperatures employed for complex decomposition are in the range of 50 to 129 F. 'Since there is no advantage in employing higher temperatures for complex decomposition, it is ordinarily eiected at atmospheric temperature.

The extract phase containing phenol coniis ordinarily equivalent `to the volume oi.e the Yextract solution washed; volume ratios of wash to extract solution between Ul kand 2 are prescribed. The removal of hexamethylene tetrarnine `from the extract phase prevents resin formation on heat stripping `of the .decomposition solvent from `the phenolic compounds and `on their fractionation into individual .phenolicfcomponente.

Thiophenolic compounds 'are recovered from the `antisolvent solution of hexamethylene tetramine treated aromatic vmixture .and from the wash solution obtained on subjecting 'the liquid complex to washing with antisolvent. In countercurrent contact of phenoland :thiophenolw -containing aromatic mixture with aqueous hexn amethylene tetramine wherein washing 4with the antisolvent is eieeted in the lofvver portion of the tower, the antisolvent wash solution combines with the antisolvent solution or aromatic mixture. `Recovery of thiophenols from the antisolvent solutionis simply eiiected by vfractional distillation if the original aromatic mixture comprises only phenols and .thiophenols `since there `.is a substantial boiling point dil'erential` between an .antisolvent such as .pentane and :the `thio'- (iii phenols. If thiophenols `are recovered from 4the `antisolvent solution by `fractional distillation, it

'is advisable to :subject the .antisolvent solution to water washing prior to distillation in order to remove traces of hexame'thylene tetramine which will form condensation products with thiophenols during .the distillation step. An alternate procedure for recovering the "thiophenols from the .antisolvent `solution involves a conventional procedure :such as extraction with a caustic solution.. v'Since thiophenols are the ,only

remaining acidic compounds present in the antisolvent solution, they are isolated as a caustic jextraot from which they are sprung by acidication.

In the accompanying drawing, there is diagrammatically outlined a continuous flow for resolving a mixture containing low molecular weight phenols and thiophenolic compounds into their phenolic and thiopnenolic components.

In the diagram presented, an aqueous `slurry of hexamethylene tetrainine in the presence of `an antisolvent is used to differentiate between phenolic and thiophenolic compounds.

A mixture of phenols and thiophenols which is a fraction of coal tar distillate boiling between 35i) and 480 F., and which is hereafter termed aromatic oil, is introduced through a pipe I into the middle portion of ia tower 2 which acts as a coniplexing, separating and washing zone. Approximately an equal volume of pentane antisolvent is introduced into the lower portion of the tower 2 through a `pipe ,3 while an aqueous .slurry of 4hexamethyiene tetramine is introduced into the upperportion ofthe tower 2 througha pipe fi.

lCountercurrent contact of the pentane solution of aromatic oil containing low molecular weight phenols and thiophenols with theaqueous slurry of hexamethylene tetramine results in the formationof hexamethylene tetramine ,complexes of 'the low molecular weight phenols which separate as a distinct liquid phase which is intermediate in density between the pentane solution of aromatic oil and the aqueous slurry of hexamethylene tetrainine so that it forms the middle layer. of a static system.

There is withdrawn from the upper portion *of the tower 2 througha pipe l a pent-ane solution of aromatic oil which contains substantially all ofthethiophenolspresent in the original feed, but whose content of low molecular weight phenols is verysmalL The pentane solution of thio- .phenohoontaining aromatic oil is introduced into a washitower 8 wherein it issubjected to counteryafter to recover the hexarnethylene tetramine therefrom.

'The water-washed .pentane solution of thio- 'phenolic aromatic oil is removed from the wash tower 8 through a pipe if! `and is introduced into a towerl wherein pentane is reinovedby stripping. Pentane is taken on overhead through 'a .pipe l and is recycled therethrough to a pipe 3 through which it isintroduced into the tower 2.

From the .bottom `portion of the tower l5 through-a pipe il, .there Yis withdrawn .an aromatic `oil containing 'thiophenols `If the low not been suftlciently reduced eration, as described, reduces is withdrawn from tower 5| through a pipe molecular weight phenolic content of this oil has by once-through operation, it can be recycled to the tower 2. Under normal operation conditions, once-through opthe low molecular weight phenolic content to a sufficiently low level. The thiophenols can be recovered from the aromatic oil by conventional caustic extraction.

The aqueous slurry of hexamethylene tetramine and the liquid complex phase flowing downwardly through the tower 2 are washed free of thiophenols and other aromatic impurities by contact with pentane in the lower portion of the tower 2. The pentane-washed mixture of aqueous hexamethylene tetramine slurry and liquid complex phase is withdrawn from the tower 2 through a pipe 39 and is introduced into a tower 3i wherein it is extracted with ether which is introduced into the tower 3l through a pipe 32. Contact of the composite mixture of complex phase and aqueous slurry with ether eiects decomposition oi the complex into its components with extraction of the thiophenol-free low molecular weight phenols in the ether extract phase and the suspension of the hexamethylene tetramine in the aqueous slurry.

The hexamethylene tetramine slurry is withdrawn from the bottom of the tower 3| through a pipe 35, stripped of ether in the stripper 36 and recycled to the contact tower 2 through a pipe 31. Stripped ether is recycled to tower 3i through pipes 38 and 32.

The ether extract phase containing thiophenolfree low molecular weight phenolic compounds is removed from the upper portion of tower 3l through a pipe 45 and introduced into a wash tower 46 wherein it is subjected to counter-current washing with water introduced therein through a pipe 4l with resulting removal oi dissolved hexamethylene tetrarnine therefrom. Wash water containing a small percentage of hexamethylene tetramine, approximately 1 to 4 per cent, iswithdrawn from the wash tower 4S through a pipe 48, combined with the wash water obtained from washing of the pentane solution of thiophenol-containing aromatic oil in the tower 8. rlhe combined wash waters are introduced into a stripper t wherein both ether and Y water are stripped therefrom to obtain an aqueous slurry of hexamethylene tetramine which can be recycled to the contacting zone. The ether is removed from the stripper 5t through a pipe 51 while wateris removed therefrom through a pipe 52. The aqueous hexamethylene tetramine slurry obtained in the stripping operation is removed from the bottom of the stripper 50 and is recycled through pipes 53 and 31 to the contact tower 2. Y

The water-washed extract ether phase containing thiophenol-free low molecular weight phenols the wash tower 46 through a pipe @il and is introduced into a stripping tower El for removal of ether. Ether is taken oi from the stripping tower El through a pipe 62 and is recycled therethrough to the extraction tower 3|.

Low molecular weight phenols comprising phenol, cresols, ethylphenols and xylenols are withdrawn from the bottom of the stripping 63. These low molecular weight phenols which are free from thiophenols can be resolved into individual components by fractional distillation.

The following example illustrates the use of the process of this invention in resolving the mixture of phenols and thiophenols. In this example, the separation process of the invention is applied to an aromatic acid oil consisting predominantly of phenols and thiophenols which have been obtained by acidification of an aqueous caustic solution obtained on caustic scrubbing of petroleum naphtha.

200 cc. of an aromatic acid oil distilling between 350 and 450 F. and obtained by acidiiication of an aqueous caustic extract resulting from caustic scrubbing of petroleum naphtha was diluted with 500 cc. or" pentane and then contacted with 1,200v cc. oi" an aqueous saturated hexamethylene tetramine solution. The reaction mixture settled to form a B-phase liquid system comprising a pentane-rich phase, a complex-rich phase and an aqueous hexamethylene tetraminerich phase. The pentane-rich phase was separated from the complex phase and the aqueous hexamethylene tetramine phase, was waterwashed and stripped of pentane to yield 43 cc. of a thiophenol-rich fraction which analyzed 21.7 weight per cent sulfur as compared with 5.45 per cent sulfur content of the original aromatic acid oil. The combined aqueous and complex-rich phases were subjected to washing with pentane to yield a pentane wash from which there was obtained after water washing and stripping an additional 10 cc. of a thiophenol-rich concentrate which analyzed 19.1 weight per cent sulfur.

The pentane-washed combined aqueous and complex-rich phases were extracted with an equal volume of ether to yield an ether extract which was washed with an equal volume of water and stripped of ether to yield 118 cc. of a thiophenolfree concentrate comprising low molecular weight phenolic compounds. This phenol-rich concentrate only analyzed 0.23 weight per cent sulfur, as contrasted with the 5.45 per cent sulfur content of the original aromatic acid oil.

The foregoing example clearly illustrates the effectiveness of this invention in resolving a mixture of phenols and thiophenols. The low sulfur content of the phenol fraction and the high sulfur content of the thiophenol concentrate prove that excellent resolution of the mixture has been effected in the batch operation described. A continuous countercurrent system effects even better resolution.

While the oil treated in the foregoing example comprises predominantly phenols and thiophenols, it is apparent that the process of the invention is applicable to the separation of phenols from thiophenols in mixtures such as coal tar distillate, wherein low molecular weight phenols and thiophenols are associated withl a large amount of neutral aromatic compounds such as alkylbenzenes.

Obviously many modiiications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof, and, therefore, only such limitations should he imposed as are indicated in the appended claims.

We claim:

1. A process for separating low molecular weight phenolic compounds of the group consisting of phenol, cresols, ethylphenois and xylenols from thiophenol and its homologs which comprises contacting a mixture containing said phenolic and thiophenolic compounds with hexamethylene tetramine at a temperature below 180 F., separating said reaction mixture in the presence of an antisolvent selected from the group consisting ci parainio and naphthenic hydrocarbons and mixtures thereof into an antihigh solvent power for phenols and a low solvent power for hexamethylene tetramine and water at a temperature below 180 F. whereby there is formed an extract phase containing said low molecular weight phenols, recovering said phenols from said extract phase and recovering thiophenols from said antisolvent solution.

2. A process according to claim l in which decomposition of the complex phase is eiiected with an ether.'

3. A process according to claim 1 in which solid anhydrous hexamethylene tetramine is the complexing agent.

4. A process according to claim 1 in which aqueous hexamethylene tetramine is the complexing agent.

5. A process for separating low molecular weight phenolic compounds of the group consisting of phenol, cresols, ethylphenols and xylenols from thiophenol and its homologs which comprises contacting a mixture containing said phenolic and thiophenolic compounds with hexamethylene tetramine at a temperature below 180 F. in the presence of an antisolvent selected from the group consisting of paraflinic and naphthenic hydrocarbons and mixtures thereof, said contact resulting in the formation of thiophenol-containing anti-solvent solution and a distinct liquid complex phase consisting mainly of complexes of said hexamethylene tetramine and said low molecular weight phenols, separating said complex phase from said antisolvent solution, decomposing complex phase into hexamethylene tetramine and low molecular weight phenolic compounds substantially free of thiophenolic compounds by extraction with an oxygenated hydrocarbon having a high solvent power for phenols and a low solvent power for hexamethylene tetramine and water at a temperature below 180 F. whereby there is formed an extract phase con taining said low molecular weight phenols, recovering said phenols from said extract phase and recovering thiophenols from said antisolvent solution.

6. A process according to claim 5 in which aqueous hexamethylene tetramine is the complexing agent.

7. A process according to claim 5 in which solid anhydrous hexamethylene tetramine is the complexing agent.

8. A process according to claim 5 in which decomposition of the complex is eiected extraction with an ether.

9. A process according to claim 5 in which said separated complex phase is washed with anti solvent prior to its decomposition by extraction with an oxygenated hydrocarbon.

10. A process according to claim 5 in which the phenol-ccntaining extract phase is water washed prior to recovery of phenols therefrom.

1l; A process according to claim 5 in which said antisolvent solution is water washed pricil to recovery of thiophenols therefrom.

12. A process according to claim 5 in which pentane is used as the antisolvent.

13. A process according to claim 5 in winch contact of said phenoland thiophcnol-containing mixture with hexamethylene tetramine in the presence of said antisolvent and decomposition of said complex are effectedat a temperature between 50 and 120 F.

14. A process according to claim 5 in which the antisolvent is a parafnic hydrocarbon oontaining 3 to 10 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,779,715 Scott Oct. 28, 1930 1,955,023 Roos et al Apr. 17, 1934 2,184,928 Luten et al. Dec. 26, 1939 2,310,616 Cislal et al. Feb. 9, 1943 

1. A PROCESS FOR SEPARATING LOW MOLECULAR WEIGHT PHENOLIC COMPOUNDS OF THE GROUP CONSISTING OF PHENOL, CRESOLS, ETHYLPHENOLS AND XYLENOLS FROM THIOPHENOL AND ITS HOMOLOGS WHICH COMPRISES CONTACTING A MIXTURE CONTAINING SAID PHENOLIC AND THIOPHENOLIC COMPOUNDS WITH HEXAMETHYLENE TETRAMINE AT A TEMPERATURE BELOW 180* F., SEPARATING SAID REACTION MIXTURE IN THE PRESENCE OF AN ANTISOLVENT SELECTED FROM THE GROUP CONSISTING OF PARAFFINIC AND NAPHTHENIC HYDROCARBONS AND MIXTURES THEREOF INTO AN ANTISOLVENT SOLUTION AND A DISTINCT LIQUID COMPLEX PHASE CONSISTING MAINLY OF HEXAMETHYLENE TETRAMINE AND SAID LOW MOLECULAR WEIGHT PHENOLIC COMPOUNDS, DECOMPOSING SAID COMPLEX PHASE INTO HEXAMETHYLENE TETRAMINE AND LOW MOLECULAR WEIGHT PHENOLIC COMPOUNDS SUBSTANTIALLY FREE OF THIOPHENOLIC COMPOUNDS BY EXTRACTION WITH A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER AND OXYGENATED HYDROCARBONS HAVING A HIGH SOLVENT POWER FOR PHENOLS AND A LOW SOLVENT POWER FOR HEXAMETHYLENE TETRAMINE AND WATER AT A TEMPERATURE BELOW 180* F. WHEREBY THERE IS FORMED AN EXTRACT PHASE CONTAINING SAID LOW MOLECULAR WEIGHT PHENOLS, RECOVERING SAID PHENOLS FROM SAID EXTRACT PHASE AND RECOVERING THIOPHENOLS FROM SAID ANTISOLVENT SOLUTION. 